Silanyl phenols and naphthols

ABSTRACT

There are described silanyl phenols and naphthols of formula (1 a ) or (1 b ), wherein R 1  is hydrogen; halogen; hydroxy; C 1 –C 20 alkyl; C 3 –C 12 cycloalkyl; C 1 –C 20 alkoxy; trifluoromethyl; pentafluoroethyl; mono- or di-C 1 –C 5 alkylamino; hydroxy-C 1 –C 5 alkyl; or phenyl, phenyl-C 1 –C 20 alkyl, phenoxy, phenyl-C 1 –C 20 alkoxy, naphthyl or naphthyl-C 1 –C 20 alkyl each unsubstituted or substituted by C 1 –C 5 alkyl, C 3 –C 12 cycloalkyl, C 1 –C 5 alkoxy, C 3 –C 12 cycloalkoxy, halogen, oxo, carboxy, carboxy-C 1 –C 7 alkyl ester, carboxy-C 3 –C 12 cycloalkyl ester, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C 1 –C 20 alkylamino or by nitro; R 2 , R 3  and R 4  are each independently of the others hydrogen; C 1 –C 20 alkyl; or C 3 –C 12 -cycloalkyl; R 5 , R 6  and R 7  are each independently of the others C 1 –C 20 alkyl, C 5 –C 10 aryl, C 1 –C 20 alkoxy, phenyl-C 1 –C 20 alkyl, phenyl-C 1 –C 20 alkoxy, C 2 –C 5 alkenyl, —O—Si—(C 1 –C 5 alkyl) 3 ; or O—Si—(C 1 –C 5 alkyl) 2 -O—Si(C 1 –C 5 alkyl) 3  and n is 0 or 1. The compounds exhibit a pronounced activity against Gram positive and Gram negative bacteria, and also against yeasts and moulds

The present invention relates to selected silanyl phenols and naphthols,to the preparation of such compounds, to the use of such compounds forthe antimicrobial treatment of surfaces, as antimicrobial activeingredients against Gram-positive and Gram-negative bacteria, yeasts andfungi and in the preservation of cosmetics, household products,textiles, plastics, and for use in disinfectants.

The compounds according to the invention correspond to the formula

wherein

-   R₁ is hydrogen; halogen; hydroxy; C₁–C₂₀alkyl; C₃–C₁₂cycloalkyl;    C₁–C₂₀alkoxy; trifluoromethyl pentafluoroethyl; mono- or    di-C₁–C₅alkylamino; hydroxy-C₁–C₅alkyl; or phenyl,    phenyl-C₁–C₂₀alkyl, phenoxy, phenyl-C₁–C₂₀alkoxy, naphthyl or    naphthyl-C₁–C₂₀alkyl each unsubstituted or substituted by    C₁–C₅alkyl, C₃–C₁₂cycloalkyl, C₁–C₅alkoxy, C₃–C₁₂cycloalkoxy,    halogen, oxo, carboxy, carboxy-C₁–C₇alkyl ester,    carboxy-C₃–C₁₂cycloalkyl ester, cyano, trifluoromethyl,    pentafluoroethyl, amino, N,N-mono- or di-C₁–C₂₀alkylamino or by    nitro;-   R₂, R₃ and R₄ are each independently of the others hydrogen;    C₁–C₂₀alkyl; or C₃–C₁₂-cycloalkyl;-   R₅, R₆ and R₇ are each independently of the others C₁–C₂₀alkyl,    C₅–C₁₀aryl, C₁–C₂₀alkoxy, phenyl-C₁–C₂₀alkyl, phenyl-C₁–C₂₀alkoxy,    C₂–C₅alkenyl, —O—Si—(C₁–C₅alkyl)₃; or    —O—Si—(C₁–C₅alkyl)₂-O—Si(C₁–C₅alkyl)₃ and-   n is 0 or 1,    there not being included compounds of formula (1a) wherein-   R₁, R₂, R₃ and R₄ are hydrogen and R₅, R₆ and R₇ are simultaneously    methyl.

C₁–C₂₀Alkyl denotes straight-chain or branched alkyl radicals, e.g.methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl,amyl, isoamyl or tert-amyl, heptyl, octyl, isooctyl, nonyl, decyl,undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl or eicosyl.

C₁–C₂₀Alkoxy denotes straight-chain or branched radicals, e.g. methoxy,ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy,isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy,pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy or eicosyloxy.

C₃–C₁₂Cycloalkyl denotes e.g. cyclopropyl, cyclobutyl, cyclopentyl,cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl,cyclodocecyl and especially cyclohexyl.

In the context of the definitions given, alkenyl includes inter aliavinyl, allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl,n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl,isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.

C₅-C₁₀Aryl denotes phenyl or naphthyl.

Preference is given to compounds of formula (1a) or (1b), wherein

-   R₁ is hydrogen; C₁–C₂₀alkyl; C₁–C₂₀alkoxy; or phenyl, phenoxy,    phenyl-C₁–C₂₀alkyl, phenyl-C₁–C₂₀alkoxy, naphthyl or    naphthyl-C₁–C₂₀alkyl each unsubstituted or substituted by    C₁–C₅alkyl, C₃–C₁₂cycloalkyl, C₁–C₅alkoxy, C₃–C₁₂cycloalkoxy,    halogen, oxo, carboxy, carboxy-C₁–C₇alkyl ester,    carboxy-C₃–C₁₂cycloalkyl ester, cyano, trifluoromethyl,    pentafluoroethyl, amino, N,N-mono- or di-C₁–C₂₀alkylamino or by    nitro.

Especially preferred compounds of formula (1a) or (1b) are those wherein

-   R₁ is hydrogen, C₁–C₂₀alkyl, C₁–C₂₀alkoxy, phenyl, or phenoxy    unsubstituted or substituted by halogen, C₁–C₅alkyl or by    cyclo-C₅–C₇alkyl;    and especially those wherein-   R₁ is hydrogen; C₁–C₂₀alkyl; C₁–C₅alkoxy; phenyl or phenoxy.-   R₂, R₃ and R₄ in formula (1 a) or (1b) are preferably each    independently of the others hydrogen or methyl.-   R₅, R₆ and R₇ are preferably each independently of the others    hydrogen; C₁–C₂₀alkyl; C₁–C₂₀alkoxy; C₂–C₅alkenyl; C₆–C₁₀aryl;    —O—Si(C₁–C₅alkyl)₂-O—Si(C₁–C₅alkyl)₃ or —O—Si—(C₁–C₅alkyl)₃; and    especially C₁–C₅alkyl; C₁–C₂₀alkoxy; phenyl;    —O—Si(C₁–C₅alkyl)₂-O—Si(C₁–C₅alkyl)₃ or —O—Si—(C₁–C₅alkyl)₃.

Very special preference is given to compounds of formulae

wherin

-   R₁ is hydrogen; C₃–C₂₀alkyl; C₁–C₅alkoxy; phenyl; or phenoxy,-   R₂ is hydrogen; or C₁–C₅alkyl; and-   R₅, R₆ and R₇ are each independently of the others C₁–C₅alkyl;    phenyl; —O—Si(C₁–C₅alkyl)₂-O—Si(C₁–C₅alkyl)₃; or    —O—Si—(C₁–C₅alkyl)₃.

Examples of very especially preferred compounds of the inventioncorrespond to the formulae

The compounds according to the invention are prepared in very generalterms by the addition of silanes that contain at least one Si—H bond tophenols or naphthols substituted as desired that have unsaturated sidechains (hydrosilylation).

The invention relates also to the process for the preparation of silanylphenols and naphthols of formulae (1a) and (1b). In the process a phenolor naphthol compound is etherified with an allyl halide (1st step), theresulting alkenyl phenyl ether compound is rearranged to form analkenylphenyl compound (2nd step), and a silane compound that containsat least one Si—H bond is added to that compound (3rd step) according tothe following Scheme:

In that reaction scheme

-   R₁ is hydrogen; halogen; hydroxy; C₁–C₂₀alkyl; C₃–C₁₂cycloalkyl;    C₁–C₂₀alkoxy; trifluoromethyl; pentafluoroethyl; mono- or    di-C₁–C₆alkylamino; hydroxy-C₁–C₅alkyl; or phenyl,    phenyl-C₁–C₂₀alkyl, phenoxy, phenyl-C₁–C₂₀alkoxy, naphthyl or    naphthyl-C₁–C₂₀alkyl, each unsubstituted or substituted by    C₁–C₅alkyl, C₃–C₁₂cycloalkyl, C₁–C₅alkoxy, C₃–C₁₂cycloalkoxy,    halogen, oxo, carboxy, carboxy-C₁–C₇alkyl ester,    carboxy-C₃–C₁₂cycloalkoxy ester, cyano, trifluoromethyl,    pentafluoroethyl, amino, N,N-mono- or di-C₁–C₂₀alkylamino or by    nitro;-   R₂, R₃ and R₄ are each independently of the others hydrogen;    C₁–C₂₀alkyl; or C₃–C₁₂-cycloalkyl; and-   R₅, R₆ and R₇ are each independently of the others C₁–C₂₀alkyl;    C₅–C₁₀aryl; C₁–C₂₀alkoxy; phenyl-C₁–C₂₀alkyl; phenyl-C₁–C₂₀alkoxy;    C₂–C₅alkenyl; —O—Si—(C₁–C₅alkyl)₃; or    —O—Si—(C₁–C₅alkyl)₂-O—Si(C₁–C₅alkyl)₃.

The hydrosilylation is carried out according to processes known per sein an inert organic solvent, preferably at elevated temperature, in thepresence of catalytic amounts of a transition metal complex. Suitablecomplexes are, for example, generally complexes of the metals rhodium,iridium or cobalt, or especially carbonyls of the metals iron, cobalt,nickel, rhodium, ruthenium, manganese or chromium. Special preference isgiven to complexes of platinum or hexachloroplafinic acid H₂PtCl₆.

As starting compounds for the hydrosilylaton there are usedalkenyl-phenols or -naphthols, which are prepared according to processesknown per se, as described, for example, in Synthesis 1981, 310 forFriedel-Crafts allylation of phenols. The alkenyl-phenols or -naphtholsare preferably prepared from readily obtainable alkenyl phenyl ethers bya Claisen rearrangement. The rearrangement reaction can be carried outwith or without high-boiling solvents at temperatures of 200–250° C. Therearrangement is preferably carried out in ethylene glycol or itsoligomers, or ethers thereof, especially in diethylene glycol dimethylether at 220° C. in a pressurised vessel. That procedure results in anespecially pure reaction product.

The Invention relates also to compounds of formula

wherein

-   R₁ is hydrogen; halogen; hydroxy; C₁–C₂₀alkyl; C₃–C₁₂cycloalkyl;    C₁–C₂₀alkoxy; trifluoromethyl; pentafluoroethyl; di-C₁–C₅alkylamino;    hydroxy-C₁–C₅alkyl; or phenyl, phenoxy, phenyl-C₁–C₂₀alkyl,    phenyl-C₁–C₂₀alkoxy, naphthyl or naphthyl-C₁–C₂₀alkyl each    unsubstituted or substituted by C₁–C₅alkyl, C₃–C₁₂cycloalkyl,    C₁–C₅alkoxy, C₃–C₁₂cycloalkoxy, halogen, oxo, carboxy,    carboxy-C₁–C₇alkyl ester, carboxy-C₃–C₁₂cycloalkyl ester, cyano,    trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or    di-C₁–C₂₀alkylamino or by nitro;-   R₂, R₃ and R₄ are each independently of the others hydrogen;    C₁–C₂₀alkyl; or C₃–C₁₂-cycloalkyl.

Silanyl phenols and naphthols of formula

wherein

-   R₁ is hydrogen; halogen; hydroxy; C₁–C₂₀alkyl; C₃–C₁₂cycloalkyl;    C₁–C₂₀alkoxy; trifluoromethyl; pentafluoroethyl; mono- or    di-C₁–C₅alkylamino; hydroxy-C₁–C₅alkyl; or phenyl,    phenyl-C₁–C₂₀alkyl, phenoxy, phenyl-C₁–C₂₀alkoxy, naphthyl or    naphthyl-C₁–C₂₀alkyl each unsubstituted or substituted by    C₁–C₅alkyl, C₃–C₁₂cycloalkyl, C₁–C₅alkoxy, C₃–C₁₂cycloalkoxy,    halogen, oxo, carboxy, carboxy-C₁–C₇alkyl ester,    carboxy-C₃–C₁₂cycloalkyl ester, cyano, trifluoromethyl,    pentafluoroethyl, amino, N,N-mono- or di-C₁–C₂₀alkylamino or by    nitro;-   R₂, R₃ and R₄ are each independently of the others hydrogen;    C₁–C₂₀alkyl; or C₃–C₁₂cycloalkyl;-   R₅, R₆ and R₇ are each independently of the others C₁–C₂₀alkyl,    C₅–C₁₀aryl, C₁–C₂₀alkoxy, phenyl-C₁–C₂₀alkyl, phenyl-C₁–C₂₀alkoxy,    C₂–C₅alkenyl, —O—Si—(C₁–C₅alkyl)₃; or    —O—Si—(C₁–C₅alkyl)₂-O—Si(C₁–C₅alkyl)₃ and-   n is 0 or 1,    exhibit pronounced antimicrobial activity, especially against    Gram-positive and Gram-negative bacteria and against bacteria of    skin flora, and also against yeasts and moulds. They are accordingly    especially suitable in the disinfection, deodorisation and general    and anti-microbial treatment of the skin and mucosa and of    integumentary appendages (hair), more especially in the disinfection    of hands and of wounds.

They are therefore suitable as antimicrobial active ingredients and aspreservatives in personal care preparations, for example shampoos, bathadditives, hair-care products, liquid and solid soaps (based onsynthetic surfactants and salts of saturated and/or unsaturated fattyacids), lotions and creams, deodorants, other aqueous or alcoholicsolutions, e.g. cleansing solutions for the skin, moist cleansingcloths, oils or powders.

The invention accordingly relates also to a personal care preparationcomprising at least one compound of formula (1c) and cosmeticallytolerable carriers or adjuvants.

The personal care preparation according to the invention comprises from0.01 to 15% by weight, preferably from 0.1 to 10% by weight, based onthe total weight of the composition, of the compound of formula (1c),and cosmetically tolerable adjuvants.

Depending on the form of the personal care preparation, it willcomprise, in addition to the silanyl phenol or naphthol of formula (1c),further constituents, for example sequestering agents, colourings,perfume oils, thickening or solidifying agents (consistency regulators),emollients, UV absorbers, skin-protective agents, antioxidants,additives that improve mechanical properties, such as dicarboxylic acidsand/or Al, Zn, Ca and Mg salts of C₁₄–C₂₂-fatty acids, and optionallypreservatives.

The personal care preparation according to the invention may beformulated as a water-in-oil or oil-in-water emulsion, as an alcoholicor alcohol-containing formulation, as a vesicular dispersion of an ionicor non-ionic amphiphilic lipid, as a gel, a solid stick or as an aerosolformulation.

As a water-in-oil or oil-in-water emulsion the cosmetically tolerableadjuvant preferably comprises from 5 to 50% of an oily phase, from 5 to20% of an emulsifier and from 30 to 90% water. The oily phase maycontain any oil suitable for cosmetic formulations, e.g. one or morehydrocarbon oils, a wax, a natural oil, a silicone oil, a fatty acidester or a fatty alcohol. Preferred mono- or poly-ols are ethanol,isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.

Cosmetic formulations according to the invention are used in variousfields. For example, the following preparations especially come intoconsideration:

-   -   skin-care preparations, e.g. skin-washing and cleansing        preparations in the form of tablet-form or liquid soaps,        synthetic detergents or washing pastes,    -   bath preparations, e.g. liquid (foam baths, milks, shower        preparations) or solid bath preparations, e.g. bath cubes and        bath salts;    -   skin-care preparations, e.g. skin emulsions, multi-emulsions or        skin oils;    -   cosmetic personal care preparations, e.g. facial make-up in the        form of day creams or powder creams, face powder (loose or        pressed), rouge or cream make-up, eye-care preparations, e.g.        eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix        creams; lip-care preparations, e.g. lipstick, lip gloss or lip        contour pencils, nail-care preparations, such as nail varnish,        nail varnish remover, nail hardeners or cuticle removers;    -   intimate hygiene preparations, e.g. intimate washing lotions or        intimate sprays;    -   foot-care preparations, e.g. foot baths, foot powders, foot        creams or foot balsams, special deodorants and antiperspirants        or callus-removing preparations;    -   light-protective preparations, such as sun milks, lotions,        creams, oils, sun blocks or tropicals, pre-tanning preparations        or after-sun preparations;    -   skin-tanning preparations, e.g. self-tanning creams;    -   depigmenting preparations, e.g. preparations for bleaching the        skin or skin-lightening preparations;    -   insect-repellents, e.g. insect-repellent oils, lotions, sprays        or sticks;    -   deodorants, such as deodorant sprays, pump-action sprays,        deodorant gels, sticks or roll-ons;    -   antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;    -   preparations for cleansing and caring for blemished skin, e.g.        synthetic detergents (solid or liquid), peeling or scrub        preparations or peeling masks;    -   hair-removal preparations in chemical form (depilation), e.g.        hair-removing powders, liquid hair-removing preparations, cream-        or paste-form hair-removing preparations, hair-removing        preparations in gel form or aerosol foams;    -   shaving preparations, e.g. shaving soap, foaming shaving creams,        non-foaming shaving creams, foams, gels, preshave preparations        for dry shaving, aftershaves or aftershave lotions;    -   fragrance preparations, e.g. fragrances (eau de Cologne, eau de        toilette, eau de parfum, parfum de toilette, perfume), perfume        oils or cream perfumes;    -   dental-care, denture-care and mouth-care preparations, e.g.        toothpastes, gel toothpastes, tooth powders, mouthwash        concentrates, anti-plaque mouthwashes, denture cleaners or        denture fixatives;    -   cosmetic hair-treatment preparations, e.g. hair-washing        preparations in the form of shampoos and conditioners, hair-care        preparations, e.g. pre-treatment preparations, hair tonics,        styling creams, styling gels, pomades, hair rinses, treatment        packs, intensive hair treatments, hair-structuring preparations,        e.g. hair-waving preparations for permanent waves (hot wave,        mild wave, cold wave), hair-straightening preparations, liquid        hair-setting preparations, hair foams, hair sprays, bleaching        preparations, e.g. hydrogen peroxide solutions, lightening        shampoos, bleaching creams, bleaching powders, bleaching pastes        or oils, temporary, semi-permanent or permanent hair colourants,        preparations containing self-oxidising dyes, or natural hair        colourants, such as henna or camomile.

An antimicrobial soap has, for example, the following composition:

-   0.01 to 5% by weight of the compound of formula (1c),-   0.3 to 1% by weight titanium dioxide,-   1 to 10% by weight stearic acid,-   ad 100% soap base, e.g. the sodium salts of tallow fatty acid and    coconut fatty acid or glycerols.

A shampoo has, for example, the following composition:

-   0.01 to 5% by weight of the compound of formula (1c),-   12.0% by weight sodium laureth-2-sulfate,-   4.0% by weight cocamidopropyl betaine,-   3.0% by weight NaCl and-   water ad 100%.

A deodorant has, for example, the following composition:

-   0.01 to 5% by weight of the compound of formula (1c),-   60% by weight ethanol,-   0.3% by weight perfume oil, and-   water ad 100%.

The invention relates also to an oral composition, comprising

-   0.01 to 15% by weight, based on the total weight of the composition,    of the compound of formula (1c), and orally tolerable adjuvants.

Example of an oral composition:

-   1.0% by weight sorbitol,-   10% by weight glycerol,-   15% by weight ethanol,-   15% by weight propylene glycol,-   0.5% by weight sodium lauryl sulfate,-   0.25% by weight sodium methylcocyl taurate,-   0.25% by weight polyoxypropylene/polyoxyethylene block copolymer,-   0.10% by weight peppermint flavouring,-   0.1 to 0.5% by weight of a compound of formula (1c), and-   48.6% by weight water.

The oral composition according to the invention may be, for example, inthe form of a gel, a paste, a cream or an aqueous preparation(mouthwash).

The oral composition according to the invention may also comprisecompounds that release fluoride ions which are effective against theformation of caries, for example inorganic fluoride salts, e.g. sodium,potassium, ammonium or calcium fluoride, or organic fluoride salts, e.g.amine fluorides, which are known under the trade name Olafluor.

The silanyl phenols and naphthols of formula (1c) according to theinvention are also suitable for the treatment, especially preservation,of textile fibre materials. Such materials are undyed and dyed orprinted fibre materials, e.g. of silk, wool, polyamide or polyurethanes,and especially cellulosic fibre materials of all kinds. Such fibrematerials are, for example, natural cellulosic fibres, such as cotton,linen, jute and hemp, as well as cellulose and regenerated cellulose.Preferred suitable textile fibre materials are made of cotton.

The silanyl phenols and naphthols according to the invention are alsosuitable for the treatment of plastics, especially for impartingantimicrobial properties to or preserving plastics, e.g. polyethylene,polypropylene, polyurethane, polyester, polyamide, polycarbonate, latexetc. Fields of use therefore are, for example, floor coverings, plasticscoatings, plastics container and packaging materials; kitchen andbathroom utensils (e.g. brushes, shower curtains; sponges, bathmats),latex, filter materials (air and water filters), plastics articles usedin the field of medicine, e.g. dressing materials, syringes, cathetersetc., so-called “medical devices”, gloves and mattresses.

Paper, for example papers used for hygiene purposes, may also beprovided with antimicrobial properties using the silanyl phenols andnaphthols according to the invention.

It is also possible for nonwovens, e.g. nappies/diapers, sanitarytowels, panty liners, and cloths for hygiene and household uses, to beprovided with antimicrobial properties in accordance with the invention.

The silanyl phenols and naphthols of formula (1c) are also used inwashing and cleaning formulations, e.g. in liquid and powder detergentsor fabric conditioners.

The silanyl phenols and naphthols of formula (1c) can be used especiallyalso in household and all-purpose cleaners for cleaning and disinfectinghard surfaces.

A cleaning preparation has, for example, the following composition:

-   0.01 to 5% of the compound of formula (1c)

3.0% octyl alcohol 4E0 1.3% fatty alcohol C₈–C₁₀polyglucoside 3.0%isopropanol ad 100% water.

In addition to preserving cosmetics and household products, it is alsopossible for technical products to be preserved and provided withantimicrobial properties; use as a biocide in technical processes isalso possible, for example in paper treatment, especially in papertreatment liquors, printing thickeners of starch or cellulosederivatives, varnishes and paints.

The silanyl phenols and naphthols of formula (1c) are also suitable forthe antimicrobial treatment of wood and for the antimicrobial treatmentof leather, the preservation of leather and the provision of leatherwith antimicrobial properties.

The compounds according to the invention are also suitable for theprotection of cosmetic products and household products from microbialdamage.

The following Examples illustrate, but do not limit, the presentinvention.

PREPARATION EXAMPLES

The preparation of allylphenols in diethylene glycol dimethyl ether isdescribed in general and the preparation of 2-methallyl-4-phenyl-phenol(101d), which is novel, is described in particular:

Example 1 Preparation of 4-biphenyl-methallyl Ether (Compound of Formula101c)

A mixture of 4.9 g (29 mmol) of 4-hydroxybiphenyl, 3.2 g (35 mmol) ofmethallyl chloride and 4.8 g (35 mmol) of anhydrous potassium carbonatein 100 ml of absolute DMF is stirred under nitrogen for 12 hours at 85°C. After filtration and removal of the solvent, the ether can be usedwithout further purification for the subsequent rearrangement; yield 6.0g (92% of theory).

Example 2 Preparation of 2-methallyl-4-phenyl-phenol (Compound ofFormula 101d)

2.2 g (10 mmol) of the previously prepared ether are heated at refluxunder nitrogen for 48 hours in 20 ml of o-dichlorobenzene at 180° C. Thephenol is then separated from the unreacted ether by extracting thereaction mass, which has been diluted with 50 ml of methylene chloride,several times with sodium hydroxide solution at pH 11. After customaryaqueous working-up, the product is obtained in sufficient purity for thesubsequent hydrosilylation

-   (>95 area % GC),-   Yield 1.1 g (50% of theory)-   ¹H-NMR(CDCl₃):-   6.8–7.45 (m,8H,arom.—H), 5.1 (s,1H,OH), 4.8/4.85 (s,1H,═CH), 3.35    (s,2H,CH₂), 1.7 (s,3H,CH₃)

Examples 3 to 6 Preparation of Further o-allylphenols

General Preparation of o-allylphenols in Diethylene Glycol DimethylEther:

Approximately 25 mmol of the appropriate allyl phenyl ether are stirredin 10 ml of dry diethylene glycol dimethyl ether in a pressurised vesselfor 12 hours at 220° C. The mixture is then diluted with approximately40 ml of petroleum ether and washed twice with water. The isolated crudeproduct is purified by distillation at 10⁻² mbar. The expectedstructures are confirmed by GC/MS and ¹H-NMR.

Yield Compound of (% of formula Structure theory) ¹H-NMR (II)

50 (CDCl₃): 6.8–7.45 (m, 8H, arom.-H), 5.1(s, 1H, OH), 4.8/4.85 (s, 1H,═CH), 3.35(s, 2H, CH₂), 1.7 (s, 3H, CH₃) (III)

86 (DMSO-d₆): 9.06(s, 1H, OH), 6.76–7.24(m, 3H, arom.-H), 4.72/4.82(s,1H, ═CH), 3.32(s,2H, PhCH₂), 1.77(s, 3H, CH₃), 1.32(s, 9H, CCH₃) (IV)

78 (DMSO-d₆): 9.02(s, 1H, OH), 6.66–6.82(m, 3H, arom.-H), 5.88–5.99(m,1H, ═CH),4.98/5.02(dd, 2H, ═CH₂), 3.24(d, 2H, PhCH₂),2.16(s, 3H, CH₃)(V)

75 (DMSO-d₆): 8.76(s, 1H, OH), 6.52–6.66(m, 3H, arom.-H), 5.82–5.95(m,1H, ═CH),4.93/4.97(dd, 2H, ═CH₂), 3.58(s, 3H, CH₃),3.19(d, 2H, PhCH₂)

Examples 7 to 27 Hydrosilylation of o-allylphenols

According to the varying r activity of the types of silanes used, thehydrosilylations are carried out according to two similar procedures,which will be described hereinbelow by way of example. Yield and ¹H-NMRdata are then given in Table form. With the exception of the compound offormula (106), all the compounds are novel.

Examples 7 to 23 Hydrosilylation of o-allylphenols in Toluene

2.9 mmol of the appropriate allylphenol are dissolved under nitrogen in10 ml of absolute toluene together with a drop of Karstedt catalyst(platinum complex in divinyl-tetramethyl-disiloxane) and heated to 80°C. At that temperature, 3.5 mmol of the appropriate silane are addeddropwise and then the mixture is stirred for a further 5 hours at thattemperature. After cooling and removal of the solvent, finally under ahigh vacuum, the residue is purified by flash chromatography over silicagel (eluant: toluene). The products are obtained in the form of pale,viscous oils, and GC/MS and ¹H-NMR agree with the expected structures(Table 2):

TABLE 2 Yield (% of Compound of theory, based ¹H-NMR (CDCl₃) formulaStructure on phenol) [ppm] (101)

45% 6.7–7.25(m, 8H, arom.-H), 4.9(s, 1H, OH),2.55/2.25(dd, 1H, PhCH),1.85(m, 1H, CH),0.85(d, 3H, CH₃), 0.55/0.35(dd, 1H, SiCH),0(s, 18H,SiCH₃), −0.1(s, 3H, SiCH₃) (102)

72% 6.55–6.8(m, 3H, arom.-H), 5.35(s, 1H, OH),3.8(s, 3H, OCH₃), 2.45(t,2H, PhCH₂),1.55(m, 2H, PhCH₂CH₂), 0.4(t, 2H, SiCH₂),0.05(s, 18H, SiCH₃),−0.05(s, 3H, SiCH₃) (103)

54% 6.85–7.45(m, 8H, arom.-H), 5.0(s, 1H, OH),2.65/2.35(dd, 1H, PhCH),1.95(m, 1H, CH),0.9(d, 3H, CH₃), 0.55/0.4(dd, 1H, SiCH),0.05(s, 18H,SiCH₃), 0(s, 3H, SiCH₃) (104)

62% 6.65–4.05(m, 4H, arom.-H), 4.15(s, 1H, OH),2.5(t, 2H, PhCH₂),1.55(m, 2H, CH₂CH₂CH₂),0.45(t, 2H, SiCH₂), 0(s, 18H, SiCH₃),−0.1(s, 3H,SiCH₃) (105)

33% 6.65–7.05(m, 4H, arom.-H), 4.65(s, 1H, OH),2.5(t, 2H, PhCH₂), 1.6(m,2H, CH₂CH₂CH₂),0.55(t, 2H, CH₂Si), .05(s, 15H, SiCH₃),−0.05(s, 6H,SiCH₃) (106)

34% 6.7–7.25(m, 4H, arom.-H), .65(s, 1H, OH),2.55(t, 2H, PhCH₂), 1.6(m,2H, CH₂CH₂CH₂),0.55(t, 2H, CH₂Si), 0(s, 15H, SiCH₃) (107)

52% 6.65–7.5(m, 9H, arom.-H), 4.5(s, 1H, OH),2.5(t, 2H, PhCH₂), 1.55(m,2H, CH₂CH₂CH₂),0.85(t, 2H, CH₂Si), 0.2(s, 6H, SiCH₃) (108)

61% ¹H-NMR(DMSO-d₆): 8.81(s, 1H, OH), 6.61–6.93(m, 3H, arom. H), 2.37(d,2H, PhCH₂),1.87(m, 1H, CH), 1.18(s, 9H, C(CH₃)₃), 0.82(d,3H,CH₃),0.57/0.27(dd, 1H, SiCH),0(s, 18H, SiCH₃), −0.07(s, 3H, SiCH₃)13C ok(109)

88% ¹H-NMR(DMSO-d₆): 8.81(s, 1H, OH), 6.56–6.72(m, 3H, arom.-H), 2.4(t,2H, PhCH₂),2.08(s, 3H, CH₃), 1.46(m, 2H, CH₂CH₂),0.40(t, 2H, CH₂Si),0(s, 18H, Si(CH₃)₃),−0.08(s, 3H, SiCH₃)13C ok (110)

51% ¹H-NMR(DMSO-d₆): 8.62(s, 1H, OH), 6.45–6.65(m, 3H, arom.-H), 3.57(s,3H, OCH₃),2.42(t, 2H, PhCH₂), 1.47(m, 2H, CH₂CH₂),0.40(t, 2H, CH₂Si),0(s, 18h, Si(CH₃)₃),−0.08(s, 3H, SiCH₃)13C ok (111)

42% ¹H-NMR(DMSO-d₆): 8.44(s, 1H, OH), 6.30–7.30(m, 8H, arom.-H), 3.40(s,3H, OCH₃),2.26(t, 2H, PhCH₂), 1.30(m, 2H, CH₂CH₂),0.53(t, 2H, CH₂Si),0(s, 6H, SiCH₃)13C ok (112)

30% ¹H-NMR(DMSO-d₆): 9.43(s, 1H, OH), 6.68–6.98(m, 3H, arom.-H), 2.46(t,2H, PhCH₂),1.50(m, 2H, CH₂CH₂), 0.49(t, 2H, CH₂Si),0(s, 15H, SiCH₃,−0.06(s, 6H, SiCH₃)13C ok (113)

42% ¹H-NMR(DMSO-d₆): 8.81(s, 1H, OH), 6.59–6.92(m, 3H, arom.-H),2.29/2.44(dd, 1H, PhCH), 1.89(m, 1H, CH₃CH),1.16(s, 9H, C(CH₃)₃),0.81(d, 3H, CHCH₃),0.39/0.62(dd, 1H, CHSi), 0(s, 15H, SiCH₃),−0.08(s,6H, SiCH₃)13C ok (114)

53% ¹H-NMR(DMSO-d₆): 8.83(s, 1H, OH), 6.58–6.76(m, 3H, arom.-H), 2.43(t,2H, PhCH₂),2.10(s, 3H, CH₃), 1.48(m, 2H, CH₂CH₂),0.49(t, 2H, CH₂Si),0(s, 9H, SiCH₃), −0.01(s, 6H, SiCH₃)13C ok (115)

70% ¹H-NMR(DMSO-d₆): 9.46(s, 1H, OH), 6.67–7.04(m, 3H, arom.-H), 2.47(t,2H, PhCH₂),1.50(m, 2H, CH₂CH₂), 0.48(t, 2H, CH₂Si),0(s, 9H, SiCH₃),−0.01(s, 6H, SiCH₃)13C ok (116)

65% ¹H-NMR/DMSO-d₆): 8.85(s, 1H, OH), 7.1–8.15(m, 6H, arom.-H), 2.75(t,2H, PhCH₂),1.55(m, 2H, CH₂CH₂), 0.45(t, 2H, CH₂Si), 0(s,18H, SiCH₃),−0.1(s, 3H, SiCH₃) (117)

75% ¹H-NMR(DMSO-d₆): 8.85(s, 1H, OH), 7.1–8.15(m, 6H, arom.-H), 2.6(d,2H, PhCH₂),1.95(m, 1H, CH), 0.85(d, 3H, CH₃), 0.6/0.35(dd, 1H, SiCH),0(s, 18H, SiCH₃), −0.1(s, 3H, SiCH₃)

Examples 24 to 27 Hydrosilylation of o-allylphenols in Xylene

2.9 mmol of the appropriate allylphenol are dissolved under nitrogen in10 ml of absolute xylene together with a drop of Karstedt catalyst(platinum complex in divinyl-tetramethyl-disiloxane) and 3.5 mmol of theappropriate silane. The reaction mixture is maintained at reflux for 48hours. After cooling and removal of the solvent, finally under a highvacuum, the residue is purified by flash chromatography over silica gel(eluant: xylene). The products are obtained in the form of pale, viscousoils, and GC/MS and ¹H-NMR agree with the expected structures (Table 3):

TABLE 3 Yield (% of Compound of theory, based ¹H-NMR (CDCl₃) formulaStructure on phenol) [ppm] (118)

41% — (119)

29% ¹H-NMR(CDCl₃): 6.48–7.34(m, 8H, arom.-H),4.42(s, 1H, OH), 2.39(t,2H, PhCH₂), 1.45(m, 2H, CH₂CH₂CH₂), 0.65(t, 2H, CH₂Si), 0.1(s, 6H,SiCH₃)13C ok (120)

25% ¹H-NMR(DMSO-d₆): 8.94(s, 1H, OH), 6.41–7.22(m, 13H, arom.-H).2.09/2.24(dd, 1H, PhCH), 1.69(m, 1H, CH₃CH), 0.56(d, 3H, CH₃),0.40/0.65(dd, 1H, CHSi), 0(s, 6H,SiCH₃)13C ok (121)

37% ¹H-NMR(DMSO-d₆): 8.65(s, 1H, OH), 6.8–7.95(m, 11H, arom.-H),2.45/2.35(dd, 1H, PhCH), 1.75(m, 1H, CH),0.75/0.45(dd, 1H, CHSi), 0.6(d,3H, CH₃),0(s, 6H, SiCH₃)

Example 28 Determination of the Minimum Inhibitory Concentration (MIC)in the Agar Incorporation Test (MIC Test)

Medium: casein/soybean flour peptone agar (Merck) *Sabouraud 4% glucoseagar (Merck) Dilution medium: sterile 0.85% NaCl solution Testorganisms: Staphylococcus aureus ATCC 9144 Escherichia coli NCTC 8196Pseudomonas aeruginosa CIP A-22 Candida albicans ATCC 10231 *Aspergillusniger ATCC 6275 Incubation: 24 hours at 37° C. *3 days at 28° C. Testsolution: 1% stock solutions of all the test substances in a suit- ablesolvent are prepared and diluted in serial dilutions to finalconcentrations of from 1000 ppm to 10 ppm.Test Principle:

0.3 ml of each dilution stage is mixed with 15 ml of still-liquidnutrient medium. After the nutrient medium has solidified, 10 μl of eachof the following organism dilutions of the test strains in 0.85% NaClsolution are spotted onto the agar medium:

Staphylococcus aureus ATCC 9144 1:100 dilution Escherichia coli NCTC8196 1:1000 dilution Pseudomonas aeruginosa CIP A-22 1:1000 dilutionCandida albicans ATCC 10231 1:10 dilution Aspergillus niger ATCC 62751:10 dilution

The plates are incubated for 24 hours at 37° C. (A. niger 3 days at 28°C.) and then the highest dilution (lowest concentration) of the testsubstance at which growth is just no longer discernible (corresponds tothe MIC) is determined.

The results are shown in Tables 3a and 3b.

TABLE 3a MIC values in ppm Compound of formula Microorganisms (101)(102) (118) (104) Staphylococcus aureus 1000 >1000 4 8 ATCC 9144Escherichia coli NCTC 8196 >1000 >1000 >1000 >1000 Pseudomonasaeruginosa >1000 >1000 >1000 >1000 CIP A-22 Candida albicans ATCC10231 >1000 >1000 >1000 >1000 Aspergillus niger ATCC6275 >1000 >1000 >1000 >1000

TABLE 3b MIC values in ppm Compound of formula Microorganisms (103)(105) (107) (106) Staphylococcus aureus >560 15.6 1.9 7.8 ATCC 9144Staphylococcus hominis >560 >1000 7.8 31.2 DSM 20328 Corynebacteriumxerosis 17.5 3.9 1.9 7.8 ATCC 373 Enterococcus hirae ATCC 10541 >56015.6 3.9 15.6 Escherichia coli NCTC 8196 >560 >1000 >1000 >1000Pseudomonas aeruginosa >560 >1000 >1000 >1000 CIP A-22 Candida albicansATCC 10231 >560 >1000 125 >1000 Aspergillus niger ATCC 6275 >560 >100015.6 31.2

TABLE 3c MIC values in ppm Compound of formula Microorganisms (108)(109) (110) (119) (111) Staphylococcus aureus 0 15 250 4 125 ATCC 9144Corynebacterium xerosis 8 4 4 2 8 ATCC 373 Escherichia coliNCTC >1000 >1000 >1000 >1000 >1000 8196 Pseudomonasaeruginosa >1000 >1000 >1000 >1000 >1000 CIP A-22 Candida albicansATCC >1000 >1000 >1000 62 >1000 10231 Aspergillus nigerATCC >1000 >1000 >1000 62 >1000 6275

TABLE 3d MIC values in ppm Compound of formula Microorganisms (112)(120) (113) (114) (115) Staphylococcus aureus 7 8 >1000 8 15 ATCC 9144Corynebacterium xerosis 2 4 62 8 8 ATCC 373 Escherichia coliNCTC >1000 >1000 >1000 >1000 250 8196 Pseudomonasaeruginosa >1000 >1000 >1000 >1000 >1000 CIP A-22 Candida albicansATCC >1000 >1000 >1000 >1000 500 10231 Aspergillus nigerATCC >1000 >1000 >1000 >1000 500 6275

TABLE 3e MIC values in ppm Compound of formula Microorganisms (121)(116) (117) Staphylococcus aureus ATCC 9144 >1000 >1000 >1000Staphylococcus hominis DSM 20328 >1000 >1000 >1000 Corynebacteriumxerosis ATCC 373 250 500 1000 Escherichia coli ATCC10536 >1000 >1000 >1000 Candida albicans ATCC 1023 >1000 >1000 >1000Aspergillus niger ATCC 6275 >1000 >1000 >1000

The results show a strong antimicrobial activity of the test substancesagainst Gram-positive and Gram-negative bacteria and against fungi andyeasts.

1. A process for the preparation of a compound of formula

wherein a phenol or naphthol compound is etherified with an allyl halide(1st step), the resulting alkenyl phenyl ether compound is rearranged toform an alkenylphenyl compound (2nd step), and a silane compound thatcontains at least one Si—H bond is added to that compound according tothe following Scheme:

wherein R₁ is hydrogen; halogen; hydroxy; C₁–C₂₀alkyl; C₃–C₁₂cycloalkyl;C₁–C₂₀alkoxy; trifluoromethyl; pentafluoroethyl; mono- ordi-C₁–C₅alkylamino; hydroxy-C₁–C₅alkyl; or phenyl, phenyl-C₁–C₂₀alkyl,phenoxy, phenyl-C₁–C₂₀alkoxy, naphthyl or naphthyl-C₁–C₂₀alkyl eachunsubstituted or substituted by C₁–C₅alkyl, C₃–C₁₂cycloalkyl,C₁–C₅alkoxy, C₃–C₁₂cycloalkoxy, halogen, oxo, carboxy,carboxy-C₁–C₇alkyl ester, carboxy-C₃–C₁₂cycloalkyl ester, cyano,trifluoromethyl, pentafluoroethyl, amino N,N-mono- ordi-C₁–C₂₀alkylamino or by nitro; R₂, R₃ and R₄ are each independently ofthe others hydrogen; C₁–C₂₀alkyl; or C₃–C₁₂-cycloalkyl; R₅, R₆ and R₇are each independently of the others C₁–C₂₀alkyl; C₅–C₁₀aryl;C₁–C₂₀alkoxy; phenyl-C₁–C₂₀alkyl; phenyl-C₁–C₂₀alkoxy, C₂–C₅alkenyl;—O—Si—(C₁–C₅alkyl)₃; or —O—Si—(C₁–C₅alkyl)₂-O—Si(C₁–C₅alkyl)₃ and n is 0or 1, there not being included compounds of formula (1a) wherein R₁, R₂,R₃ and R₄ are hydrogen and R₅, R₆ and R₇ are simultaneously methyl orethyl.
 2. A method for the antimicrobial treatment of a surface, whichcomprises contacting said surface with an antimicrobially effectiveamount of a silanyl phenol or naphthol compound of formula

wherein R₁ is hydrogen; halogen; hydroxy; C₁–C₂₀alkyl; C₃–C₁₂cycloalkyl;C₁–C₂₀alkoxy; trifluoromethyl; pentafluoroethyl; mono- ordi-C₁–C₅alkylamino; hydroxy-C₁–C₅alkyl; or phenyl, phenyl-C₁–C₂₀alkyl,phenoxy, phenyl-C₁–C₂₀alkoxy, naphthyl or naphthyl-C₁–C₂₀alkyl eachunsubstituted or substituted by C₁–C₅alkyl, C₃–C₁₂cycloalkyl,C₁–C₅alkoxy, C₃–C₁₂cycloalkoxy, halogen, oxo, carboxy,carboxy-C₁–C₇alkyl ester, carboxy-C₃–C₁₂cycloalkyl ester, cyano,trifluoromethyl, pentafluoroethyl, amino, N,N-mono- ordi-C₁–C₂₀alkylamino or by nitro; R₂, R₃ and R₄ are each independently ofthe others hydrogen; C₁–C₂₀alkyl; or C₃–C₁₂-cycloalkyl; R₅, R₆ and R₇are each independently of the others C₁–C₂₀alkyl; C₅–C₁₀aryl;C₁–C₂₀alkoxy; phenyl-C₁–C₂₀alkyl; phenyl-C₁–C₂₀alkoxy; C₂–C₅alkenyl;—O—Si—(C₁–C₅alkyl)₃; or —O—Si—(C₁–C₅alkyl)₂-O—Si(C₁–C₅alkyl)₃; and n is0 or
 1. 3. A method according to claim 2, wherein the compound offormula (1c) is used in the antimicrobial treatment, deodorisation anddisinfection of the skin, mucosa and hair.
 4. A method according toclaim 2, wherein the compound of formula (1c) is used in the treatmentof textile fibre materials.
 5. A method according to claim 2, whereinthe compound of formula (1c) is used in preservation.
 6. A methodaccording to claim 2, wherein the compound of formula (1c) is used inwashing and cleaning formulations.
 7. A method according to claim 2,wherein the compound of formula (1c) is used in imparting antimicrobialproperties to and preserving plastics, paper, nonwoyens, wood orleather.
 8. A method according to claim 2, wherein the compound offormula (1c) is used in imparting antimicrobial properties to andpreserving technical products.
 9. A method according to claim 2, whereinthe compound of formula (1c) is used as a biocide in technicalprocesses.
 10. A personal care preparation, comprising from 0.01 to 15%by weight, based on the total weight of the composition, of the compoundof formula (1c) defined according to claim 2, and cosmetically tolerableadjuvants.
 11. An oral composition, comprising from 0.01 to 15% byweight, based on the total weight of the composition, of the compound offormula (1c) defined according to claim 2, and orally tolerableadjuvants.